(2S)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-[(4-methoxyphenyl)methoxymethoxy]propanal | 138436-31-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (2S)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-[(4-methoxyphenyl)methoxymethoxy]propanal
• CAS: 138436-31-4
• 化学式: C₂₉H₃₆O₅Si
• 分子量: 492.687
• InChiKey: MTSRUANVYIIYLX-VWLOTQADSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.58
• 重原子数：
  35
• 可旋转键数：
  14
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2S)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-[(4-methoxyphenyl)methoxymethoxy]propanal 在 4 Angstroem MS 、 二异丁基氢化铝 、 magnesium bromide 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 0.17h， 生成 (2S,3S)-1-<(tert-Butyldiphenylsilyl)oxy>-2-<<<(p-methoxybenzyl)oxy>methoxy>methyl>-5-hexen-3-ol
  参考文献：
  名称：

  使用DIBALH / MgBr 2系统，由保护基控制的非对映选择性还原衍生自THYM *的双保护α，α-双（羟甲基）酮

  摘要：

  新型手性结构单元THYM * 1和BHYMA * 2衍生的双保护α，α-双（羟甲基）酮5的还原反应具有良好的立体选择性（从85:15至97：3）。通过采用DIBALH和MgBr的组合两个保护基团和适当的选择2 ·的Et 2 O.

  DOI：

  10.1016/s0040-4039(00)73940-2
• 作为产物：
  描述：

  (S)-(E)-1-<(tert-Butyldiphenylsilyl)oxy>-2-<<<(p-methoxybenzyl)oxy>methoxy>methyl>-5-methylhex-3-ene 在 臭氧 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 (2S)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-[(4-methoxyphenyl)methoxymethoxy]propanal
  参考文献：
  名称：

  Chemoenzymic preparation of asymmetrized tris(hydroxymethyl)methane (THYM*) and of asymmetrized bis(hydroxymethyl)acetaldehyde (BHYMA*) as new highly versatile chiral building blocks

  摘要：

  A series of asymmetrized tris(hydroxymethyl)methanes 2 and bis(hydroxymethyl)acetaldehydes 3 have been prepared in both enantiomeric forms through a chemoenzymatic methodology. The key step is the highly enantioselective PPL-catalyzed monohydrolysis of 2(E)-alkenyl-1,3-diacetoxypropanes 25-27. A careful study on the effect of unsaturations adjacent to the prochiral center in a series of 2-substituted 1,3-diacetoxypropanes has confirmed the suggested beneficial effect of a pi-system in that position but has also unveiled an unprecedented dramatic effect of double-bond configuration on enantioselectivity. A new empirical model for the interpretation of these and other results, based both on polarity and steric arguments, is proposed. This study provides a general protocol for the efficient synthesis of asymmetrized 1,3-propanediols bearing in position 2 saturated or unsaturated carbon chains.

  DOI：

  10.1021/jo00031a039

文献信息

• Synthesis of both top and bottom fragments of (-)-talaromycin A through enantiospecific and diastereoselective elaboration of asymmetrized tris (hydroxymethyl)methane
  作者：Giuseppe Guanti、Luca Banfi、Enrica Narisano、M. Teresa Zannetti

  DOI：10.1021/jo00058a036

  日期：1993.3

  Asymmetrized tria(hydroxymethyl)methane equivalents of general formula 5 have been employed as chiral building blocks for the enantiospecific and diastereoselective synthesis of both fragments 3 and 4, whose conversion into Talaromycin A was already reported. Preparation of bottom half fragment 3 was achieved through a ''protecting group-controlled'' stereoselective allylation of an asymmetrized bis(hydroxymethyl)acetaldehyde with allyltributyltin, while the top half fragment 4 was obtained in high overall yield by sequential elongation of two of the three synthetically equivalent masked hydroxymethyl group of 5, via nucleophilic substitution reactions.
• Protecting group controlled diastereoselective allylation of asymmetrized bis (hydroxymethyl)acetaldehydes (BHYMA*)
  作者：Giuseppe Guanti、Luca Banfi、Enrica Narisano

  DOI：10.1016/0040-4039(91)80449-g

  日期：1991.11

  MgBr2 catalysed allylation of a series of diprotected asymmetrized bis (hydroxymethyl)acetaldehydes 2 with allyltributylstannane proceeds with good diastereoselectivity. The stereochemical results are in line with a cyclic chelated transition state, where only one of the two CH2OR appendages, due to the different nature of protecting groups, is capable of coordinating the Lewis acid.
• Asymmetric synthesis of all 8 stereoisomers of α-methyl homoallylic alcohols derived by crotyl addition onto bis(hydroxymethyl)acetaldehydes (BHYMA*)
  作者：Giuseppe Guanti、Luca Banfi、M.Teresa Zannetti

  DOI：10.1016/s0040-4039(00)73941-4

  日期：1993.1

  The asymmetric synthesis of epimeric alpha-methyl homoallylic alcohols 4 and 7 has been realized respectively through chelation-controlled addition of crotyltributyltin to asymmetrized bis(hydroxymethyl)acetaldehydes (BHYMA*) 3, and via chelation-controlled reduction of ketones 8. Due to the stereochemical flexibility of the C-5 chiral centre and to the enantiodivergent preparation of both enantiomers of 3, all 8 isomers of these crotylation products become accessible, starting from an unique precursor 1.
• Chemoenzymic preparation of asymmetrized tris(hydroxymethyl)methane (THYM*) and of asymmetrized bis(hydroxymethyl)acetaldehyde (BHYMA*) as new highly versatile chiral building blocks
  作者：Giuseppe Guanti、Luca Banfi、Enrica Narisano

  DOI：10.1021/jo00031a039

  日期：1992.2

  A series of asymmetrized tris(hydroxymethyl)methanes 2 and bis(hydroxymethyl)acetaldehydes 3 have been prepared in both enantiomeric forms through a chemoenzymatic methodology. The key step is the highly enantioselective PPL-catalyzed monohydrolysis of 2(E)-alkenyl-1,3-diacetoxypropanes 25-27. A careful study on the effect of unsaturations adjacent to the prochiral center in a series of 2-substituted 1,3-diacetoxypropanes has confirmed the suggested beneficial effect of a pi-system in that position but has also unveiled an unprecedented dramatic effect of double-bond configuration on enantioselectivity. A new empirical model for the interpretation of these and other results, based both on polarity and steric arguments, is proposed. This study provides a general protocol for the efficient synthesis of asymmetrized 1,3-propanediols bearing in position 2 saturated or unsaturated carbon chains.
• Protecting group controlled diastereoselective reduction of diprotected α,α-bis(hydroxymethyl)ketones derived from THYM*, using the DIBALH / MgBr2 system
  作者：Giuseppe Guanti、Luca Banfi、Renata Riva、M.Teresa Zannetti

  DOI：10.1016/s0040-4039(00)73940-2

  日期：1993.1

  The reduction of diprotected α,α-bis(hydroxymethyl)ketones 5, derived from the novel chiral building blocks THYM* 1 and BHYMA* 2 has been realized with good to excellent stereoselectivity (from 85:15 to 97:3), through a appropriate choice of the two protecting groups and by employing the combination of DIBALH and MgBr2·Et2O.

  新型手性结构单元THYM * 1和BHYMA * 2衍生的双保护α，α-双（羟甲基）酮5的还原反应具有良好的立体选择性（从85:15至97：3）。通过采用DIBALH和MgBr的组合两个保护基团和适当的选择2 ·的Et 2 O.